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Published March 17, 2010 | Supplemental Material
Journal Article Open

Synthesis of a Molecular Charm Bracelet via Click Cyclization and Olefin Metathesis Clipping


We describe the synthesis of a polycatenated cyclic polymer, a structure that resembles a molecular charm bracelet. Ruthenium-catalyzed ring-opening metathesis polymerization of an aminocontaining cyclic olefin monomer in the presence of a chain transfer agent generated an α,ω-diazide functionalized polyamine. Cyclization of the resulting linear polyamine using pseudo-high-dilution coppercatalyzed click cyclization produced a cyclic polymer in 19% yield. The click reaction was then further employed to remove linear contaminants from the cyclic polymer using azide- and alkyne-functionalized scavenging resins, and the purified cyclic polymer product was characterized by gel permeation chromatography, ^1H NMR spectroscopy, and IR spectroscopy. Polymer hydrogenation and conversion to the corresponding polyammonium species enabled coordination and interlocking of diolefin polyether fragments around the cyclic polymer backbone using ruthenium-catalyzed ring-closing olefin metathesis to afford a molecular charm bracelet structure. This charm bracelet complex was characterized by ^1H NMR spectroscopy, and the catenated nature of the small rings was confirmed using two-dimensional diffusion-ordered NMR spectroscopy.

Additional Information

© 2010 American Chemical Society. Published In Issue March 17, 2010. Article ASAP February 16, 2010. Received: October 22, 2009. We thank Professor Daniel J. O'Leary, Dr. David VanderVelde, Dr. Andrew J. Boydston, Dr. John. B. Matson, and Yan Xia for helpful discussions. The work was supported by the Office of Naval Research through its MURI program and the NSF (NSF CHE-0809418). W.Y.C. acknowledges the NSERC of Canada for a postdoctoral fellowship.

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Supplemental Material - ja9090337_si_001.pdf


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